Dyestuffs



Patented Nov. 8, 1938 1 UNITED, STATES DYESTUFFS Hans J ohner and Grald Bonhote, Basel, Switzerland, assignors to the firm Society of Chemical Industry in Basle, Basel,

application July 12, 1937, Divided and this applica- No Drawing. Original Serial No. 153,279.

tion January 10, 1938, Serial No. Switzerland July 14, 1936 Switzerland 8 Claims. (01. 260-308) termediate products for the manufacture of dyestuffs. It comprises the new arylides, the process of producing the same as well as their application for the manufacture of dyestuffs. 1 r t It has been found that valuable arylides of p-ketone-carboxylic acids may be obtained if amino compounds of the general formula in which R stands for an aryl radical of the henzene or naphthalene series such as the 5-amino- 2-phenyl-pseudo-azimidobenzene, the S-amino- 6-methyl-2-phenyl-pseudoazimidobenzene, the 5-amino-2 (4-methoxy) phenyl-pseudo-azimidobenzene, the 5-amino-2- (4'- ethoxy) -phenylpseudo azimidobenzene, the 5-amino-6-methyl- 2- (4' -met hoxy) phenyl-pseudo-azimidobenzene, the 5-amino 6 methyl-2 -(4 --ethoxy) phenylpseudo-azimidobenzene, the 5-amino-6-methoxy- 2- (4' methoxy) -phenyl-pseudo-azimidobenzene, the 5-amino-6 methoxy-2-(4' ethoxy) -phenylpseudo-azimidobenzene, the 5-amino-2-(1'lnaphthyl-pseudo-azimidobenzene, the 5-amino- 2- (4'- B-methoxy-oxy-ethyl) -phenyl-pseudo-azimidobenzene, are condensed with esters of 3- ketone-carboxylic acids, such as ethyl acetoacetate, benzoyl acetic ester, or terephthaloyl acetic ester. f y

These arylides thus correspond to the general formula" in which R stands for a member of the group F consisting of aryl nuclei ofv the benzene and naphthalene series, R1 stands for a member of the group constisting of methyl and phenyl, and 1,! stands for a' member of the group consisting of H, CH3 and O-alkyl. Among such products those are valuable in which R represents a nucleus of the benzene series because they lead to particularly valuable dyestuffs. Among such products those are again particularly valuable which correspond to the general formula in which y has the signification alreadyindicated above and :1; stands for a member of the group consistingof H, CH3 and O-alkyl. All these products are light colored powders insoluble in water but soluble in aqueous caustic alkalies.

The new arylides, which represent valuable intermediate products for the manufacture of dyestuffs, dissolve in aqueous caustic alkalies owing to the presence of the -COCH2-CO- group. In such solutions the alkali salts of the new arylides possess a marked affinity for the vegetable fiber, which is entirely surprising, since the similar arylides from the isomeric'amino-azimides do not possess such an aifinity for the vegetable fiber. Since theycombine with diazo compounds to azo-dyestuffs they are inter alia very suitable for the production of azo-dyestuffs on the vegetable fiber (cotton, ramie, flax, jute and the like) as well ason regenerated cellulose (viscose or cuprammonium silk), and also on animal fibers such as wool, natural silk or loaded silk, according to the methods usual in dyeing with ice colors. Such methods are, for example, padding the fiber in an alkaline solution of the new arylide and developing with a diazo compound, preferably one containing no hydroxy-, carboxyor sulfogroups. Such diazo-compounds are, for instance, those derived from aniline, ethers or esters of amino-phenols, for example orthoor paraanisidine, 4-chloro-Z-amino-diphenylether, 4:4- dichloro-2-aminodiphenylether; those derived from monoacylated products from 2:5-diaminohydroquinone-diethylor -dimethylether and benzoylchloride or phenoxy-acetic-acid-chloride; aminoazo-dyestuffs, for instance, 4-amino-5- methoxyazobenzene, 4-amino-2 5-dimethoxyazobenzene, 'ortho-amino-azo-toluene; further those derived from chlorotoluidines, for instance 4- chloro-2-methyl-1 aminobenzene, 4-chloro-1- methyl-Z-aminobenzene; those from nitralines such as ortho-nitraniline," l-amino-Z-methylinitrobenzene, 1-amino-2-nitrol-chlorobenzene, l-amino-2.-nitro-4-methylor -methoxybenzene, or 4-nitro-2-methoxy-1-aminobenzene; those derived from orthoor meta-chloraniline, 2:5- dichloraniline, aor c-naphthylamine and the like.

For the purpose of producing fast tints on the fiber preparations or printing colors containing them may also be prepared which contain an alkali salt of the new derivatives and a stabilized diazo-compound in the form of anitrosamine or of a diazoamino-compound. These preparations may be printed on the fiber and then developed to dyestuffs by suitable treatment, for example by passage through an acid. It is also possible to print mixtures of the free diazotizing com ponents or thecorresponding N-nitramines and alkali salts of the new coupling components on the fiber and to convert such mixture into dyestuffs by development with nitrous acid, and, if desired, subsequent treatment in alkali.

The condensation product of the general formula N NE- Aim e-R1 R N H II 0 N y in which R, R1 and 11 have the signification indicated above, coupled in substance with the same non-sulfonated compounds with which they are used for the production of fast tints on the fiber, yield pigments which are useful as such-or in coloring lacquers, varnishes or the like.

With sulfonated diazo-compounds wool dyestuffs are in particular obtained. Especially valuable are the dyestufis which are derived from ortho-hydroxylated or ortho-carboxylated diazowhich time the alcohol formed and some chlorobenzene are distilled. When condensation is complete, the mass is cooled, the chlorobenzene n is distilled in steam and the condensation product left behind is filtered; it is dissolved in dilute caustic alkali lye and, after filtration from some impurities, the solution is treated with dilute hy drochloric acid to reprecipitate the condensation product.

It is a white powder freely soluble in dilute alkalies and melting after recrystallization from alcohol at 152 C.

The process is similar with the other pseudoazimides and ,o-ketone-carboxylic acid esters cited in the introductory paragraphs. The following table shows the melting point of some of such condensation products:-

fl-ketone-carboxylic-acid-ester Az-irnide Melting point from Ethyl acetoacetate +amino-2-(4'-methoxy)-phenyl-pseudo-az-imido-benzene Alcohol 163 0. Do +5-amino-2-(4-ethoxy)-phenyl-pseudo-azimidmbenzene Alcohol 191 ,0. Do +5-amino-6-methyl-2-phenyl-pssudo-azimido-benzene Alcohol 205 .0. Do +5-amino-6-methyl-2-(4.-methoxy) -phenyl-pseudo-azi- Ohloro-benzene 222 C- Inidobenzene. v +5-amino-6-methoxy-2- (4-met hoxy) -phenyl-pseudo-azi- Alcohol 168 C.

midobenzene. +5 amino -6-metl 1oxy-2- (4 -ethoxy) phenyl-pseudo azi- Alcohol 155 C.

. midobenzene. Do +5-amino-G-chloro-2-phenyl-pseudo-azimidobenzene Alcohol 185 0. Do +5-a1nino-6-methyl-2- (1) -naphthyl-pseudo-azimidoben- Ohloro-benzene 209 0- zone. Benzoyl acetic ester +5-amino-2-pl1enyl-pseudo-azimidobenzene Alcohol 180 C. Terephthaloyl-di-acetic ester do Alcohol 280 C.

compounds as these products may be converted in substance or on the fiber into metalliferous dyestufis.

The dyestuffs which may be prepared according to the present process, with aid of the new arylides correspond therefore to the general formula let-Cate,

in which R, R1 and 1 have the signification indicated above, and R2 stands for an aromatic radical selected from the group consisting of aromatic nuclei of the benzene and naphthalene series. If these dyestufis do not contain sulfogroups they represent yellow to orange or brownorange pigments which are insoluble in water. Particularly valuable are the dyestufis of the formula in which R2 stands for an aromatic radical of the benzene series, if the benzene radical R2 contains a nitro-group in ortho-position to the N=N group. These dyestuffs when produced on the fiber dye the same yellow tints of very good fasti esftproperties, particularly excellent fastness to The following examples illustrate the invention, the parts being by weight:-

Example 1 21 parts of 5-amino-2-phenyl-pseudo-azimidobenzene are introduced into 200 parts of chlorobenzene, a few drops of diethylaniline are added and the whole is heated to boiling under reflux. The chlorobenzene is then distilled and there are added gradually 15 parts of ethylacetoacetate. C n a on "is continued for 2 hours, during Example 2 Example 3 v Cotton yarn is impregnated with a grounding prepared bydissolving 3 parts of thecondensation product from 5-aminophenyl-pseudoeazimi, dobenzene and ethylacetoacetate in 300 parts of hot water with the addition of 6 parts sodium hydroxide solution of 30 per cent. strength, 10 parts of Turkey red oil, parts of sodium chloride, and water to make up 1000 parts. The goods are then wrung out and developed in a diazo -solution which has been neutralized with sodium acetate and acidified with acetic acid, and corresponds with 2 parts of ,1-amino-2-methyl-4-nitrobenzene per 1000 parts. There is produced a pure greenish-yellow of very good properties of fastness.

The formula of the new dyestufi is:

Similar tints areobtained with other diazo-components, for instance l-amino+2-methyl-4-chlorobenzene, 1-amino-2-nitro-4-chlorobenzene, 1- amino-2-nitro-4-methylbenzene. Redder tints are obtained for instance with 1amino.-2-nitro-' 4-methoxybenzene or ortho aminoazotolune. The formula of the latter new dyestuff is:--

The goods may also be grounded at a raised temperature, for instance at 80 C.; such arylides may also be used for printing.

The following table comprises a number of other dyeing colors which may be made by this in which'R stands for a member of the group consisting of nuclei of the benzene and naph- EH w thalene series, R1 stands for a member of the group consisting of methyl and phenyl, y stands for a member of the group consisting of H, CH3 and O-alkyl, and R2 stands for an aromatic radical of the group consisting of nuclei of the heninvention:- zene and naphthalene series, which products are Diem-component Condensation product from ethyl aeeto acetate with- Color 1. Ortho-nitraniline 5-amino-2-(4-methoxy)-phenyl-pseudo-az1midobenzene Yellow. 2. l-amino-Z-nitro-4-methyl-benzene do Do. 3. l-amino-Z-nitro-i-methoxyben- Do. 4. Do. 5. Para-nitraniline Greenjsh-yellewl 6. l-amino-2-nitre-4-methoxybenzene. o RBddlSlI-YBHOW. 7. Ortho-aminoazo-toluene s. 5-amino-6-methyl-2-phenyl-pseudo dobenzene Gold-orange. 8. l-amino-Z-nitro-4-ehlorbenzene. 5-a3mino-6-methyl-2-(4-methoxy)- henyl-pseudo-azimido- Reddish-yellow.

enzene. 9. 2:5-diehloraniline 5-aamino-6-methoxy-2-(4-methexy)-phenyl-pseudo-azimido- Yellow.

enzene. 10. 4:4-diChlor-Z-amiuodiphenylether do Greenish-yellow. l1. l-amino-2-nitro-4-chlorbenzene.- do-.- Reddlsh-yellow. 12. Ortho-nitraniline Yellow.

The dyestuffs Nos. 1, 3, 6 and 9 of the foregoing table correspond to the following formulaszyellow to orange powders dyeing the fiber yellow to orange tints.

2. As new products the unsulfonated dyestuffs of the general formula N t f No-cHo-cm 1 om-o-O- I H 0 N I ll 7 NCCHC--CH: s. OKs-CON N 1 n i N-O0H-C-CH: e. CzHrO-O-N l V N=N-OOOH1 11 o N I II II N-o-oH-o-crn 9 CHrO-- -'N o --OOHa What 'we claim is:- 1. As new products the dyestuffs of the general formula in which R, stands for .a member of the group 5. As new products the unsulfonated dyestuffs consisting of nuclei of the benzene and naphof the general formula thalene series, R1 stands for a member of the roup consisting of methyl and phenyl, :1; stands H 0 for a member of the group consisting of H, CH3 I ll ll and O-alkyl, and R2 stands for an aromatic N O OH 'C radical of the group consisting of nuclei of the s benzene and naphthalene series, which products are yellow to orange powders dyeing the fiber yellow to orange tints.

in WhlCh R stands for a nucleus of the benzene of3hAs nrew lilllldgl il l the unsulfonated dyestufis series, y stands for a member of the group con- 8 ge era 0 m sisting of H, CH3 and O-alkyl, and R2 stands N for a nucleus of the benzene series containing a nitro group, which products are yellow to orange R powders, dyeing the fiber yellow to orange tints.

\ z 6. The dyestufi of the formula N in which R stands for a nucleus of the benzene H 0 0 series, R1 stands for a member of the group conl H O sisting of methyl and phenyl, 1/ stands for a mem- I N C TH-C CH ber of the group consisting of H, CH3 and O-alkyl, I No and R2 stands for a nucleus of the benzene series, which products are yellow to orange powders dye- E ing the fiber yellow to orange tints. 3 4. As new products the unsulfonated dyestuffs of the general formma 7. The dyestufi Of the formula H o N g CH J CH 7 N I ll I? RN\ N=N R2 0H3 OGN/ N 0 CH 0 on,

V N in which R stands for a nucleus of the benzene N V series, 1 stands for a member of the group con- N 2 sisting of H, CH3 and O-alkyl, and R2 stands for a nucleus of the benzene series, which products 8. The dyestuff of the formula I N 1 I? I? --N-o-cHo--om G I 40 N=NO CH;

N02 are yellow to orange powders dyeing the fiber A S OH ER.

yellow to orange tints. GERALD VBONHOTE. 

